Spiral Spin Order Research Articles

Spin Dynamics and Phonons in Chromites CoCr2O4 and MnCr2O4

Abstract Due to the geometric magnetic frustration inherent to their lattice and the resulting complex magnetic states, the spinel compounds are of great interest in both fundamental and application-oriented perspectives. Here, we applied x-ray diffraction, magnetization, heat capacity and powder inelastic neutron scattering measurements, along with theoretical calculations, to study the exotic properties of chromite-spinel oxides, CoCr2O4 and MnCr2O4. The temperature dependence of the phonon spectra provides an insight into the correlation between oxygen motion and the magnetic order, as well as the magnetoelectric effect in the ground state of MnCr2O4. Moreover, spinwave excitations in CoCr2O4 and MnCr2O4 are compared with Heisenberg model calculations. This approach enables the precise determination of exchange energies and offers a comprehensive understanding of the spin dynamics and relevant exchange interactions in complicated spiral spin ordering.

Signatures of polarized chiral spin disproportionation in rare earth nickelates

In rare earth nickelates (RENiO3), electron-lattice coupling drives a concurrent metal-to-insulator and bond disproportionation phase transition whose microscopic origin has long been the subject of active debate. Of several proposed mechanisms, here we test the hypothesis that pairs of self-doped ligand holes spatially condense to provide local spin moments that are antiferromagnetically coupled to Ni spins. These singlet-like states provide a basis for long-range bond and spiral spin order. Using magnetic resonant X-ray scattering on NdNiO3 thin films, we observe the chiral nature of the spin-disproportionated state, with spin spirals propagating along the crystallographic (101)ortho direction. These spin spirals are found to preferentially couple to X-ray helicity, establishing the presence of a hitherto-unobserved macroscopic chirality. The presence of this chiral magnetic configuration suggests a potential multiferroic coupling between the noncollinear magnetic arrangement and improper ferroelectric behavior as observed in prior studies on NdNiO3 (101)ortho films and RENiO3 single crystals. Experimentally-constrained theoretical double-cluster calculations confirm the presence of an energetically stable spin-disproportionated state with Zhang-Rice singlet-like combinations of Ni and ligand moments.

Jahn–Teller effect driven dielectric anomaly and intrinsic magnetodielectric behaviors in nickel chromate

Some spinel chromium oxides with the chemical formula ACr2O4 exhibit magnetic-induced multiferroicity due to the special spiral spin order. However, because of the relatively low temperature of the ordered spiral phase, this kind of multiferroicity generally displays a limited coexistence of magnetic and ferroelectric orders in a narrow temperature range. The Jahn–Teller (JT) effect, serving as a crucial link between charge and orbit degrees of freedom, can facilitate efficient modulation of multiferroic properties. In this work, Ni1−xCuxCr2O4 (0 ≤ x ≤ 0.2) series are synthesized by occupying the same Wyckoff site with two kinds of JT ions. The microstructure and JT distortion can be distinctly influenced by varying the doping level of Cu2+ ions. Particularly, Ni0.85Cu0.15Cr2O4 (x = 0.15) presents the pronounced JT distortion, accompanied by observation of dielectric anomaly at ∼78 K, resulting from spin–orbit coupling. This implies that the JT effect can significantly promote the contribution of spin–orbit coupling in magnetoelectric correlation. Moreover, the magnetodielectric effect induced by intrinsic magnetoelectric coupling is confirmed in Ni0.85Cu0.15Cr2O4 over a wide temperature range of 10–200 K, which is much higher than the Néel temperature of ∼85 K. It indicates that spin–orbit coupling based on the JT effect could overcome the constraint of magnetic order to achieve effective control on electric polarization performance under an applied magnetic field, thereby showing broad application prospects.

Atomic-Scale Visualization of Multiferroicity in Monolayer NiI2.

Progress in layered van der Waals materials has resulted in the discovery of ferromagnetic and ferroelectric materials down to the monolayer limit. Recently, evidence of the first purely 2D multiferroic material wasreported in monolayer NiI2. However, probing multiferroicity with scattering-based and optical bulk techniques is challenging on 2D materials, and experiments on the atomic scale are needed to fully characterize the multiferroic order at the monolayer limit. Here, scanning tunneling microscopy (STM) supported by density functional theory (DFT) calculations is used to probe and characterize the multiferroic order in monolayer NiI2. It is demonstrated that the type-II multiferroic order displayed by NiI2, arising from the combination of a magnetic spin spiral order and a strong spin-orbit coupling, allows probing the multiferroic order in the STM experiments. Moreover, the magnetoelectric coupling of NiI2 is directly probed by external electric field manipulation of the multiferroic domains. The findings establish a novel point of view to analyze magnetoelectric effects at the microscopic level, paving the way toward engineering new multiferroic orders in van der Waals materials and theirheterostructures.

Electrons interacting with Goldstone modes and the rotating frame

We consider electronic systems with a spontaneously broken continuous symmetry. The scattering vertex between electrons and Goldstone modes is calculated over the entire Brillouin zone using the random phase approximation. This calculation reveals two things: (1) electrons always couple to both ϕ and ∂tϕ, where ϕ is the Goldstone field, and (2) quasiparticles in a state with continuous symmetry breaking have to be defined in a rotating frame, which locally follows the fluctuations of the order parameter. The implications of these findings for electron spectral functions in both symmetry-broken and thermally disordered systems are discussed, and the examples of antiferromagnetism in the Hubbard model and spin spiral order in the three-band model are worked out in detail. Published by the American Physical Society 2024

Advancing humidity sensing and magnetocaloric properties of spinel structural CoCr2O4 nanoparticles achieved via innovative bismuth doping by combustion synthesis

This study explores the influence of Bi-doping on Co1-xBixCr2O4 (x = 0–0.2) nanoparticles synthesized via the solution combustion method, focusing on humidity sensing and magnetocaloric effects. The investigation reveals two magnetic transitions: the Curie temperature (TC) marks the paramagnetic to ferrimagnetic shift, while the spiral transition temperature (TS) indicates a spiral spin order transition. Magnetization measurements demonstrate that −ΔSM and relative cooling power (RCP) values vary with Bi concentration, making these nanoparticles viable for magnetic refrigeration above liquid nitrogen temperatures. Analyzing magnetic entropy variation, the modified Arrott plots and Kouvel-Fisher approach affirm second-order phase transitions. The sensing response exhibits growth alongside relative humidity (RH) and Bi concentration, culminating in an impressive ∼97.56 % sensing response for the 20 % Bi-doped sample. This heightened humidity sensing performance with increased Bi content can be attributed to synergistic effects. These results highlight the potential of 20 % Bi-doped Co1-xBixCr2O4 nanoparticles as promising contenders for enduring and practical humidity sensing applications.

Incommensurate Spiral Spin Order in CaMn2Bi2 Observed via High-Pressure Neutron Diffraction.

High-pressure neutron diffraction is employed to investigate the magnetic behavior of CaMn2Bi2 in extreme conditions. In contrast to antiferromagnetic ordering on Mn atoms reported at ambient pressure, our results reveal that at high pressure, incommensurate spiral spin order emerges due to the interplay between magnetism on the Mn atoms and strong spin-orbit coupling on the Bi atoms: sinusoidal spin order is observed at pressures as high as 7.4 GPa. First-principles calculations with a noncollinear spin orientation demonstrate band crossing behavior near the Fermi level as a result of strong hybridization between the d orbitals of Mn and the p orbitals of Bi atoms. Competing antiferromagnetic order is observed at different temperatures in the partially frustrated lattice. Theoretical models have been developed to investigate spin dynamics. This research provides a unique toolbox for conducting experimental and theoretical magnetic and spin dynamics studies of magnetic quantum materials via high-pressure neutron diffraction.

Atomic‐Scale Modulation of Synthetic Magnetic Order in Oxide Superlattices

Atomic-scale precision control of magnetic interactions facilitates a synthetic spin order useful for spintronics, including advanced memory and quantum logic devices. Conventional modulation of synthetic spin order has been limited to metallic heterostructures that exploit Ruderman-Kittel-Kasuya-Yosida interaction through a nonmagnetic metallic spacer; however, they face issues arising from Joule heating and/or electric breakdown. The practical realization and observation of a synthetic spin order across a nonmagnetic insulating spacer will lead to the development of spin-related devices with a completely different concept. Herein, the atomic-scale modulation of the synthetic spiral spin order in oxide superlattices composed of ferromagnetic metal and nonmagnetic insulator layers is reported. The atomically controlled superlattice exhibits an oscillatory magnetic behavior, representing the existence of a spiral spin structure. Depth-sensitive polarized neutron reflectometry evidences modulated spiral spin structures as a function of the nonmagnetic insulator layer thickness. Atomic-scale customization of the spin state can move the field one step further to actual spintronic applications.

Enhanced magnetoelectric effect by spin-orbit coupling in M-type hexaferrite

Magnetoelectric (ME) effect triggered by spiral spin orders in various hexaferrites develops both the theory and application of ME coupling. However, the strength of such ME effect is restricted by the small spin-orbit coupling (SOC) of $3d$ electrons in M-type hexaferrite. Here, we introduce the $5d$ element Ir with large SOC into $\mathrm{Sr}{\mathrm{Fe}}_{12}{\mathrm{O}}_{19}$. It is found that a low ${\mathrm{Ir}}^{4+}\text{\ensuremath{-}}\mathrm{doping}$ level (about 4.2% of total ${\mathrm{Fe}}^{3+}$ ions) can induce conical spin order in $\mathrm{Sr}{\mathrm{Mg}}_{x}{\mathrm{Ir}}_{x}{\mathrm{Fe}}_{12\ensuremath{-}2x}{\mathrm{O}}_{19}$ ceramics, mainly because ${\mathrm{Ir}}^{4+}$ ions prefer to enter a crucial $4{f}_{2}$ magnetic-interacted site and thus strengthen the local Dzyaloshinskii-Moriya interaction. Spin-order-induced polarization $({P}_{\mathrm{spin}})$ is achieved and displays a synchronous temperature-dependent behavior with the displacive polarization $({P}_{\mathrm{disp}})$. This interesting ME effect is discussed via $d\text{\ensuremath{-}}p$ hybridization emerging at $\mathrm{Fe}{\mathrm{O}}_{5}$ trigonal bipyramids. Moreover, ${P}_{\mathrm{spin}}$ response decreases step by step during the periodical ME test, reflecting the controllable helicity and the possible multilevel states. These results demonstrate the impact of the $5d$ element with strong SOC on the formation of conical spin order and the enhancement of ME effect in M-type hexaferrite, and also reveal the interconnectedness between ${P}_{\mathrm{spin}}$ and ${P}_{\mathrm{disp}}$.

Disappearance of spiral spin order and field induced spin reorientation transition in Fe[formula omitted]Cr[formula omitted]VO[formula omitted] (0.1[formula omitted][formula omitted][formula omitted]0.3) multiferroic: 57Fe Mössbauer spectroscopic studies

Here we report a progressive suppression of spiral spin order and evidence for disappearance of spin reorientation transition (SRT) in Fe1−xCrxVO4 (0.1 ≤x≤ 0.3) studied by low temperature and high magnetic field (LTHM) Mössbauer spectroscopy (MS). Variation in the area ratio of lines 2 and 3 (A23) with external magnetic field confirms the presence of antiferromagnetic (AFM) ordering for all the compositions at the lowest temperatures (5 K). Field induced spin reorientation transition is being observed in both triclinic (x = 0.10) and mixed phase (x = 0.175) systems, evidenced by the change in the sign of quadrupole shift (QS) value at low temperatures, where as the SRT is absent in the monoclinic phase (x = 0.20 and 0.30). MS line width (Γ) values indicate the presence of spiral spin order in T-phase, partial suppression in mixed phase (T + M) and finally complete suppression for the M-phases.

Transverse instability and universal decay of spin spiral order in the Heisenberg model

We analyze the intrinsic stability of spin spiral states in the two-dimensional Heisenberg model isolated from its environment. Our analysis reveals that the SU(2) symmetric point hosts a dynamic instability that is enabled by the existence of energetically favorable transverse deformations---both in real and spin space---of the spiral order. The instability is universal in the sense that it applies to systems with any spin number, spiral wave vector, and spiral amplitude. Unlike the Landau or modulational instabilities which require impurities or periodic potential modulation of an optical lattice, quantum fluctuations alone are sufficient to trigger the transverse instability. We analytically find the most unstable mode and its growth rate, and compare our analysis with phase-space methods. By adding an easy-plane exchange coupling that reduces the Hamiltonian symmetry from SU(2) to U(1), the stability boundary is shown to continuously interpolate between the modulational instability and the transverse instability. This suggests that the transverse instability is an intrinsic mechanism that hinders long-range phase coherence even in the presence of exchange anisotropy.

Magnetoelectric coupling in Sr3Co2Fe23.04Al0.96O41 single crystal near room temperature

We have grown Z-type hexaferrite Sr3Co2Fe23.04Al0.96O41 single crystal with a little Al3+ ion doping on the Fe3+ ion sites by the Na2CO3-Fe2O3 flux method. The magnetic properties and magnetoelectric (ME) coupling effects were investigated systematically. With Al3+ ion doping, the transverse conical magnetic phase could be maintained up to 359 K under small magnetic field (H). The magnetization increases with two steps to saturation at 300 K as shown in the M-H curve, implying the existence of a spiral spin order. The ME coupling effects occur near room temperture. Besides, the sign of the electric polarization (P) is independent of the H and the intensity of the electric polarization changes without any decays at 200 K under the oscillating magnetic field. Both of them are crucial for device application, such as information storage devices and non-volatile memory.

Microscopic origins and stability of ferromagnetism in Co3Sn2S2

Based on the density functional theory, we examine the origin of ferromagnetism in the Weyl semimetal ${\mathrm{Co}}_{3}{\mathrm{Sn}}_{2}{\mathrm{S}}_{2}$ using different types of response theories. We argue that the magnetism of ${\mathrm{Co}}_{3}{\mathrm{Sn}}_{2}{\mathrm{S}}_{2}$ has a dual nature and bears certain aspects of both itineracy and localization. On the one hand, the magnetism is soft, where the local magnetic moments strongly depend on temperature and the angles formed by these moments at different Co sites of the kagome lattice, as expected for itinerant magnets. On the other hand, the picture of localized spins still remains adequate for the description of the local stability of the ferromagnetic (FM) order with respect to the transversal spin fluctuations. For the latter purposes, we employ two approaches, which provide quite different pictures for interatomic exchange interactions: the regular magnetic force theorem and a formally exact theory based on the calculation of the inverse response function. The exact theory predicts ${\mathrm{Co}}_{3}{\mathrm{Sn}}_{2}{\mathrm{S}}_{2}$ to be a three-dimensional ferromagnet with the strongest interaction operating between next-nearest neighbors in the adjacent kagome planes. The ligand states are found to play a very important role by additionally stabilizing the FM order. When the local moments decrease, the interplane interactions sharply decrease, first causing the FM order to become quasi-two-dimensional, and then making it unstable with respect to the spin-spiral order propagating perpendicular to the kagome plane. The latter instability is partly contributed by the states at the Fermi surface and may be relevant to the magnetic behavior of ${\mathrm{Co}}_{3}{\mathrm{Sn}}_{2}{\mathrm{S}}_{2}$ near the Curie temperature. Peculiarities of the half-metallic ferromagnetism in ${\mathrm{Co}}_{3}{\mathrm{Sn}}_{2}{\mathrm{S}}_{2}$ are also discussed.

Structural, microstructural and temperature dependent magnetic properties of Mg–Ni doped CoCr2O4 ceramics

In the present work, [Co(1-(x + y)) MgxNiy][Cr2]O4 (CMNCr)(where, x = y = 0, 0.10, 0.20) NPs are examine in detail by using experimental results. Solution combustion method is adopted to prepare the CMNCr NPs. Experimental results were studied to understand structure (using XRD), microstructure (using SEM) and magnetic behaviour (using SQUID). The structural analysis was confirmed a single-phase spinel cubic structure with singular structural distortions associated with Mg–Ni doping and the generation of metal vacancies. SEM micrographs of all samples reveal their highly porous nature. EDS was utilized to examine the elemental analysis of the samples. The formation of spinel cubic structure without impurity were also confirmed by Fourier-transform infrared (FTIR) spectroscopy and the same tool is used to investigate the absorption bands related to the A-site and B-site. For all samples, paramagnetic phase to ferrimagnetic phase transition observed at TC and conical spiral spin order transition observed at TS. The curie temperature is found to be 98 K, 89 K, and 85 K for [Co][Cr2]O4, [Co0.8 Mg0.1Ni0.1][Cr2]O4 and [Co0.6 Mg0.2Ni0.2][Cr2]O4 samples, respectively. The spiral transition temperature is found to be 26 K, 14 K and 8 K for [Co][Cr2]O4, [Co0.8 Mg0.1Ni0.1][Cr2]O4 and [Co0.6 Mg0.2Ni0.2][Cr2]O4 samples, respectively. All of the samples exhibit paramagnetic behaviour above TC. The negative magnetization effect were observed in [Co0.6 Mg0.2Ni0.2][Cr2]O4 NPs. 20% of Mg and 20% of Ni substitution to Co site in [Co][Cr2]O4 leads to the evident magnetization reversal at the compensation temperature with an applied magnetic field of 100 Oe. The M − H loop at 10 K exhibits large coercivity due to the spiral spin ordering. This phenomenon of negative magnetization in the material results in a stable state of magnetization in the material, which has significant applications in the field of magnetic storage devices.

Oxygen deficiency in Sr2FeO4-x: electrochemical control and impact on magnetic properties.

The oxygen-deficient system Sr2FeO4-x was explored by heating the stoichiometric Fe4+ oxide Sr2FeO4 in well-defined oxygen partial pressures which were controlled electrochemically by solid-state electrolyte coulometry. Samples with x up to about 0.2 were obtained by this route. X-ray diffraction analysis reveals that the K2NiF4-type crystal structure (space group I4/mmm) of the parent compound is retained. The lattice parameter a slightly decreases while the c-parameter increases with increasing x, which is in contrast to the Ruddlesden-Popper system Sr3Fe2O7-x and suggests removal of oxygen atoms from FeO2 lattice planes. The magnetic properties were studied by magnetization, 57Fe Mössbauer, and powder neutron diffraction experiments. The results suggest that extraction of oxygen atoms from the lattice progressively changes the elliptical spiral spin ordering of the parent compound to an inhomogeneous magnetic state with coexistence of long-range ordered regions adopting a circular spin spiral and smaller magnetic clusters.

Theory of competing excitonic orders in insulating WTe2 monolayers

We develop a theory of the excitonic phase recently proposed as the zero-field insulating state observed near charge neutrality in monolayer WTe$_2$. Using a Hartree-Fock approximation, we numerically identify two distinct gapped excitonic phases: a spin density wave state for weak non-zero interaction strength and spin spiral order at stronger interactions, separated by a narrow window of non-excitonic quantum spin Hall insulator. We introduce a simplified model capturing key features of the WTe$_2$ band structure, in which these phases appear as distinct valley ferromagnetic orders. We link the competition between the excitonic phases to the orbital structure of electronic wavefunctions at the Fermi surface and hence its proximity to the underlying gapped Dirac point in WTe$_2$. We briefly discuss collective modes of the two excitonic states, and comment on implications for experiments.

Coexistence of exchange bias and memory effect in nanocrystalline CoCr2O4

This article reports exchange bias (EB) and memory effect in nanocrystalline CoCr2O4 with a detailed understanding of the origin of the observed effect. In order to investigate the EB effect in nanocrystalline CoCr2O4, two samples are synthesized with particle sizes 12 and 7 nm via sol-gel route (the second one is embedded in amorphous silica host). For both the samples, despite usual core-shell interaction or ‘surface’ domination, conventional EB effect is observed where the EB field sharply decreases with temperature and vanishes over the spiral ordering temperature (TS) of the samples. A bulk sample of the same composition, with particle size greater than 150 nm, reproducing similar characteristics, rules out the origin of EB due to surface effect. Results indicate that the exchange bias is due to inherent magnetic inhomogeneity: interaction between spiral spin order and collinear ferrimagnetic order below TS. The ac-susceptibility measurement points towards absence of surface glassiness in the sample with 12 nm particle size. However, the sample with particle size 7 nm reveals the characteristics of superspin-glass (SSG), confirmed by magnetic memory effects both in time (t) and temperature (T) dependent magnetization protocols.

Interaction-induced topological phase transition and Majorana edge states in low-dimensional orbital-selective Mott insulators

Topological phases of matter are among the most intriguing research directions in Condensed Matter Physics. It is known that superconductivity induced on a topological insulator’s surface can lead to exotic Majorana modes, the main ingredient of many proposed quantum computation schemes. In this context, the iron-based high critical temperature superconductors are a promising platform to host such an exotic phenomenon in real condensed-matter compounds. The Coulomb interaction is commonly believed to be vital for the magnetic and superconducting properties of these systems. This work bridges these two perspectives and shows that the Coulomb interaction can also drive a canonical superconductor with orbital degrees of freedom into the topological state. Namely, we show that above a critical value of the Hubbard interaction the system simultaneously develops spiral spin order, a highly unusual triplet amplitude in superconductivity, and, remarkably, Majorana fermions at the edges of the system.

Effect of Mn doping on magnetodielectric properties of polycrystalline BiFeO3 ceramics

This report reveals the room temperature magnetodielectric effect of polycrystalline BiFe0.8Mn0.2O3 ceramics. Structural analysis shows that the additional phases of BiFe0.8Mn0.2O3 are suppressed and compared with bare BiFeO3. The difference in dissociation energies between Mn–O and Bi–O bonds traps the motion of oxygen ions and reduces the grain size of BiFe0.8Mn0.2O3. Mn-doped BiFeO3 samples exhibit a weak ferromagnetic response because of the effect of Mn in the Fe site which uncurls the spiral spin ordering by altering the canting angle. Additionally, Bi vacancies give rise to charge compensating oxidation of Mn3+/ Mn4+ which causes the ferromagnetic weaker. BiFe0.8Mn0.2O3 shows an improved dielectric permittivity compared to BiFe0.9Mn0.1O3 and BiFeO3 respectively. The magnetodielectric coupling coefficient of BiFe0.8Mn0.2O3 ceramic at 6 kOe and 1 MHz is determined to be 4.64%.

Interactions in the bond-frustrated helimagnet ZnCr2Se4 investigated by NMR

The zero field 53Cr nuclear magnetic resonance was measured at low temperatures to investigate the interactions in the bond-frustrated S = 3/2 Heisenberg helimagnet ZnCr2Se4. A quadratic decrease of the sublattice magnetization was determined from the temperature dependence of the isotropic hyperfine field. We calculated the magnetization using linear spin wave theory for the incommensurate spiral spin order and compared this outcome with experimental results to estimate the coupling constants. The hyperfine fields at Cr and Se ions provide evidences that the spin polarization of Cr ions is transferred to neighboring Se ions due to the covalent bonding between them, resulting in reduced magnetic moment in the Cr ion. This observation indicates that the Jahn-Teller effect, which leads to distortion inducing spin-lattice coupling, is not completely missing in ZnCr2Se4.